Perfume compositions containing
geranonitrile, cinnamyl nitrile
or z-nonenyl nitrile

ABSTRACT

COMPOSITIONS CONTAINING GERANONITRILE TO IMPART THERETO A CITRUSY LEMON-LIKE ODOR, BUT SUBSTANTIALLY FREE FROM DISCOLORATION AND ODOR DEGRADATION. SUCH COMPOSITIONS MAY INCLUDE SOAPS OR DETERGENTS.

United States Patent Oflice Reiasued Apr. 11, 1972 27,332 PERFUMECOMPOSITIONS CONTAINING GERANONITRILE, CINNAMYL NITRILE OR 2-NONENYLNITRILE Willard T. Somerville, Monmouth, N.J., and Edward J. Shuster,Brooklyn, N.Y., assignors to International Flavors & Fragrances Inc.,New York, NY.

No Drawing. Original No. 3,325,369, dated June 13, 1967,

Ser. No. 335,071, Mar. 26, 1964, which is a continuation-in-part of Ser.No. 277,695, May 3, 1963. Application for reissue Mar. 23, 1970, Ser.No. 22,072

Int. Cl. A61k 7/00 U.S. Cl. 252-522 6 Claims Matter enclosed in heavybrackets appears in the original patent hut forms no part of thisreissue specification; matter printed in italics indicates the additionsmade by reissue.

ABSTRACT OF THE DISCLOSURE Compositions containing geranonitrile toimparfthereto a citrusy lemon-like odor, but substantially free fromdiscoloration and odor degradation. Such compositions may include soapsor detergents.

This invention relates to perfumes, and more particularly to perfumemixtures for use in soaps, cosmetics, space deodorants and the like.

Soaps and similar compositions are generally blended with perfumemixtures containing at least one ingredient selected to impart apleasing odor. [Often a ti-unsaturated aldehydes are used to impart thedesired odor.] It has been found that one of the most pleasant andacceptable odors is the fresh, citrusy, lemon-like odor which isobtained by blending citral either alone or as an ingredient in aperfume mixture in soaps and like compositions. [Other desirable odorsare imparted with other aldehydes such as cinnamaldehyde and 2-nonenylaldehyde.]

This application is a continuation-in-part of our earlier applicationSer. No. 277,695, filed May 3, 1963, now abandoned.

We have found that citral [and other such aldehydes have poor stability.Thus citral, when] incorporated in various compositions either alone orin a mixture discolors on standing and its odor becomes degraded. Theprincipal object of [the] our invention, accordingly, is to find asubstitute for p-unsaturated aldehydes such as citral] which, whilepossessing the desirable characteristics of [the aldehydes] citral canbe blended in the compositions mentioned either alone or as part of aperfume mixture without substantial deterioration with respect to odor,color or other desirable qualities.

We have found in accordance with our invention that geranonitrile, whichis a known substance having the formula has the desired citrusy,lemon-like odor of citral and when blended in compositions includingsoap, detergents, cosmetics, space deodorants and the like, showssubstantially no discoloration or degradation of odor on storage forlong periods of time.

[We have also discovered that cinnamonitrile has the qualitycharacteristic of cinnamaldehyde, but with a special green top note. Insoap and other compositions, it is decidedly superior to thecorresponding aldehyde in both color and odor stability] [in addition,we have found that Z-nonenyl nitrile has the cinnamon-likecharacteristics of the corresponding aldehyde. The fragrance quality ofthe latter, however, disappears so rapidly in all media that it isworthless as a perfume. The nitrile, however, is stable and retains itsfragrance characteristics as a perfume and in perfume mixtures when usedin compositions such as soaps, powders and others as referred to above]The invention comprises the novel products, the specific embodiments ofwhich are described hereinafter by way of example and in accordance withwhich we now prefer to practice the invention.

As produced by us geranonitrile contains approximately one-third cisform and two-thirds trans form by weight. This isomer mixture issubstantially similar in odor properties with citral, and we prefer touse it either alone or in mixtures in compositions such as thosementioned. Similar effects may be obtained if the isomer ratio is notexactly adhered to.

[Cinnamonitrile and Z-nonenyl nitrile are prepared in accordance withstandard procedures for example from the corresponding oxime and may beobtained either as pure isomers or as mixtures of cis and trans forms.Whether utilized as isomers or as mixtures, the compounds are remarkablystable in odor and color] We have found in accordance with our inventionthat [the aforesaid nitrilcs] geranonitrile may be utilized alone, asabove stated, for example in sachets for use in bureaus and in closets,and in other ways that compositions are normally employed. [They]Geranom'trile may also be employed alone or in mixtures in detergents,cosmetics, soaps, space deodorants and other formulations.

In this connection, we have found unexpectedly that geranonitrile may becombined with soaps which have an alkaline reaction in use, or in somedetergents which have an acid reaction, without changing its stabilitywith respect to color or odor. Compositions of this sort which includegeranonitrile have an extremely long shelf like, while citral, whenincluded in the same compositions, has a relatively short shelf life, asshown by the test below. [Similar results are obtained with the nitrilesmentioned above and similar nitriles] The following are examples of theperfume mixtures and soap and other formulations as we now prefer toproduce them. It is to be understood that these compositions arepreferred examples and the invention is not to be considered asrestricted thereto except as indicated in the appended claims.

Example I.Preparation of soap composition with geranonitrile A total ofgrams of soap chips were mixed with one gram of the perfume mixturegiven below until a substantially homogeneous composition was obtained.Another soap composition was identically prepared except that thegeranonitrile of the perfume mixture was replaced with three times theamount of citral. Both soap compositions mainfested a characteristiclemon-like odor despite the lesser amount of geranonitrile employed.

The perfume mixture consisted of the following ingredients in the partsby weight indicated:

Geranium bourbon 175 Citronellol 150 Geraniol 100 Phenyl ethyl alcohol90 Amyl cinnarnic aldehyde 200 Cyclamal 20 Lyral 100 Tetrahydro linalool37.5 Tetrahydro myrcenol 37.5 Linalool 75 Citronellyl acetate 125 Phenylethyl acetate 5 Phenyl acetaldehyde dimethyl acetal Cinnamic alcohol 35Terpineol 100 Linalyl acetate Musk ketone 10 Indole 10 Geranonitrile 101 Lyral is the registered trademark of International Flavors K:Fragrances, Inc. for 4-(4-methyl, d-hydroxy a1uy1)A=* cycl0- hexeneearboxyuldehyde.

Example lL-Testing of soaps containing geranonitrile Soap samples wereprepared in accordance with the procedure of Example I. One group ofsamples contained 0.33% by weight of geranonitrile, the other 1% byweight of citral. Samples from each group were kept in closed containersin an oven at 140 F. for five days, after which they were compared withduplicate samples kept in closed containers at room temperature. In allcases, soaps containing citral were discolored. The odor of citral wasalready in the process of degradation. In contrast, the soaps containinggeranonitrile were unchanged both in color and odor.

Example IlL-Preparation of detergent compositions containinggeranonitrile A total of 100 grams of a detergent were mixed with 0.15gram of the perfume mixture given below until a substantiallyhomogeneous composition was obtained. Other detergent compositions weresimilarly prepared except that the geranonitrile was replaced with threetimes the amount of citral. Both compositions manifested acharacteristic lemon-like odor of substantially equal strength despitethe lesser amount of geranonitrile used.

The compositions were identically tested in accordance with theprocedure described in Example II with the same results.

The perfume mixture used in preparing the detergents of this exampleconsisted of the following ingredients in parts by weight indicated:

Decyl aldehyde, 10% solution in diethyl phthalate 4 Terpinyl acetate 100Terpineol 40 Linalyl acetate 100 Orange oil 350 Geranyl acetate 100Geraniol Coumarin 2 Geranonitrile 3.5

Example IV.--Preparation of cosmetic powder composition containinggeranonitrile containing the geranonitrile was substantially unchangedin both color and odor.

[Example V.Testing of soap containing cinnamonitrile] [Test soap baseswere prepared using in the one case one part of cinnamaldehyde for partsof soap and in the other, one part cinnamonitrile for 100 parts of soap.The bars were tested in accordance with the procedure of Example II. Itwas found that in all cases the soap bars containing the aldehyde haddiscolored from white to yellow, and that there was an odor change andloss of strength of odor. The nitrile soap showed substantially nochange in odor or colon] [Example VL-Toilet soap composition with aperfume composition containing cinnamonitrile] [A perfume mixturecontaining the following ingredients in the parts by weight indicatedwas prepared:]

[Musk ambrette 4 Coumarin 20 Geraniol 12 Eugenol 24 Cinnamic aldehyde orcinnamo nitrile 24 Methyl diphenyl ether 24 Bois de Rose Oil 12 Lavenderspike 34 Rosemary tunisian 36 [Toilet soap bars were prepared and testedas in Example V. It was found that the aldehyde caused distinctyellowing of the soap bars and that the soap bars containing the nitrileremained white. Moreover, the bars containing the nitrile retained theiroriginal fragrance and odor balance whereas the odor balance wasnoticeably altered in the accelerated tests of toilet soap barscontaining the aldehyde] [Example VII.Liquid detergent containingcinnumonitrite] [Concentrated liquid detergents samples containing, inthe one case 0.2% by weight of cinnamonitrile and in the other 0.2% byweight of cinnamaldehyde were held at room temperature for ten days andcompared with one another. At the end of this period an examinationshowed that the nitrile imparted a more powerful cassia note than thealdehyde, and that with the nitrile there was no change from the waterwhite color of the original unperfumed liquid detergent base, while thealdehyde containing sample had changed to a lemon yellow color] [Thedetergent samples were further tested under use conditions by dissolving0.5 gram of the perfumed detergents in separate 200 gram portions ofwarm water. When each was compared with freshly prepared samples ofdetergent the detergent containing the aldehyde in water exhibitedevidence of degradation by change of the characteristic odor and loss ofsuch odor, whereas the comparable nitrile-containing compositionretained its full strong cinnamon-like odor, without loss of color,whereas the aldehyde containing composition exhibited a yellowishdiscoloration] [Example VIII.1Powder detergent containingcinnamonitrile] [A comparison experiment was carried out in whichdetergent base powder samples containing 0.2 gram of cinnamaldehyde or0.2 gram of cinnamonitrile per 100 grams of unperfumed detergent basepowder were thoroughly mixed in a high speed-rotary roller blender. Thesamples were examined after 10 days storage in closed glass containersat room temperature. It was found that the odor of the aldehyde had lostits characteristics very rapidly, and that the powder has acquired ayellowish cast. The sample containing the nitrile retained its typicalcinnamon note in full volume, and there was no change in color.]

[Example IX .-Cosmeric powder canmining cinnamonitrile] [A comparisonexperiment was carried out in which cosmetic talcum powder samplescontaining one gram of cinnamaldehyde or one gram of cinnamonitrile per100 grams of unperfumed talcum powder were thoroughly mixed in a highspeed rotary blender. The samples were stored in closed glass containersin an oven for one week at 100 F. In this medium the aldehyde note wascompletely altered and the talcum powder acquired a pale, ivory tint,whereas the nitrile retained its typical note with no discoloration ofthe powder base.]

[Example X .C0smeric p wder containing trans-2- nonenyl nitrile][Separate mixtures, used as described in the followmg paragraph, wereprepared containing one part trans- 2-nonenyl nitrile in 1,000 parts ofmethyl ionone and one part trans-Z-nonenal in 1,000 parts of the samesubstance] [Comparison experiments were carried out, in which 1% byweight of each mixture was incorporated in cosmetic talcum powder. Thecosmetic compositions were tested in the same manner as the previousexample, and it was found that there was a complete loss of the aidehydearoma, whereas in the case of the nitrile the waxy, plant-like odorpersisted at the end of the test period] [Example XL-SOap barscontaining trans-Z-nonenyi nitrile] [Separate mixtures were preparedcontaining one part trans-Z-nonenyl nitrile in 1,000 parts para tertiaryamyl cyclohexanone and one part trans-Z-nonenal in 1,000 parts of thesame substance] [These mixtures were incorporated into chips, at 1% byweight, mixed and plodded into bars. Some bars containing each perfumemixture were held at room temperature in closed containers for sevendays. Other bars containing each mixture were held in closed containersin an oven at 140 F. for the same length of time. It was found that withthe aldehyde, even with the samples held at room temperature, there wasa noticeable loss of aroma. In the accelerated tests at 140 F. the losswas practically complete. With the nitrile containing samples, in bothcases the original strength and balancing effect continued undiminished][The same tests as above were carried out using 0.1% mixtures of saidaldehyde and said nitrile in methyl ionone. The methyl ionone blend withthe aldehyde was not much different than methyl ionone alone at theconclusion of the tests. The sample with said nitrile, on the otherhand, maintained an unaltered floral and waxy note over the normal woodycharacter of the methyl ionone] [The same tests were carried out using0.1% mixtures of said aldehyde and said nitrile in diethyl phthalate.Aldehyde-containing soap bars held at 140 F. for only three days showeda marked fatty odor followed by progressive disappearance, until at theend of seven days the soap bars were almost devoid of starting odor. Thesaid nitrile-containing soaps under the same circumstances retained thetypical floral and waxy aroma] The use of [nitriles] geranonitrile incosmetic powders is an especially rigorous test of [their] itsstability, since in powders, degradation due to oxidation is acceleratedbecause of the enormous surface area of the powder.

In the standard age acceleration tests used in the above examples atemperature of 110 F. for one week is equivalent to six months atordinary temperature.

The amount of [nitrile] geranonitrile which will be effective in ourcompositions depends upon many factors, including [for example, theselected nitrile] the other ingredients present, their amounts and theeffects which are desired. We have found that perfume mixturescontaining as little as 0.02% by weight of [nitrile] geranonitrile oreven less may be usefully employed. For certain mixtures as much as 12%by weight or even higher is useful. When these perfume mixtures are usedin soaps and other products the amount is the same as is generallyemployed with ordinary perfume mixtures, i.e., from about 1% to about 3%by weight. Thus, as little as 0.0002% by Weight of [the selectednitrile] geranonitril may be employed to impart desirable aromacharacteristics to soaps, cosmetics and other products.

While the description of our invention has been given in terms of whatare presently considered the preferred embodiments, it will be obviousto those skilled in the art that various changes and modifications canbe made therein without departing from the spirit and scope of theinvention. It is the intention therefore, that the appended claims coverall such changes and modifications as fall within the spirit and scopeof the invention.

In each of the above examples:

The soap base" and soap chips" used consisted of unperfumed sodium basetoilet soap made from tallow and coconut oil.

The substance referred to as detergent powder was a powder obtained fromLever Bros. Co. being sold under the trademark Rinso.

The substance referred to as liquid detergent was a product manufacturedby Ultra Chemical Co., known as P-87 Liquid Detergent Base.

What is claimed is:

1. A perfume mixture containing an effective amount [of a nitrileselected from the group consisting] of geranonitrile [cinnamyl nitrile,2-nonenyl nitrile and mixtures thereof] characterized by substantialfreedom from discoloration and odor degradation on storage.

2. A composition comprising a soap together with a perfume mixturecontaining an effective amount [of a nitrile selected from the groupconsisting] of geranonitrile [cinnamyl nitrile, 2-noneny1 nitrile andmixtures thereof] characterized by substantial freedom fromdiscoloration and odor degradation on storage.

3. A composition comprising a detergent together with a perfume mixturecontaining an effective amount of [a nitrile selected from the groupconsistlng of] geranonitrile, [cinnamyl nitrile, 2-nonenyl nitrile andmixtures thereof] characterized by substantial freedom fromdiscoloration and odor degradation on storage.

4. A composition comprising a cosmetic together with a perfume mixturecontaining an effective amount of [a nitrile selected from the groupconsisting of] geranonitrile [cinnamyl nitrile, 2-noneny1 nitrile andmixtures thereof] characterized by substantial freedom fromdiscoloration and odor degradation on storage.

5. A composition comprising a space deodorant together with a perfumemixture containing an effective amount of [a nitrile selected from thegroup consisting of] geranonitrile [cinnamyl nitrile, 2-nonenyl nitrileand mixtures thereof] characterized by substantial freedom fromdiscoloration and odor degradation on storage.

[6. A perfume consisting of a mixture of cis and trans isomers ofgeranonitrile having a citrusy lemon-like odor substantially identicalwith that of citral but substantially free from discoloration and odordegradation] 7. A perfume mixture as defined in claim 1, wherein saidgeranonitrile consists of a mixture of cis and trans isomers ofgeranonitrile.

References Cited The following references, cited by the Examiner, are ofrecord in the patented file of this patent or the original patent.

Chemical Abstracts S4: 1281i (1960).

JEROME D. GOLDBERG, Primary Examiner

